Compositions containing werner complexes of chromium and fluorinated carboxylic acids

ABSTRACT

Oil and water repellent compositions containing Werner complexes formed from trivalent chromium and a mixture of fluorinated acids of the type RfCOOH and RfCH2COOH.

United States Patent 191 51 Sept. 23, 1975 Dear et al.

[ 1 COMPOSITIONS CONTAINING WERNER COMPLEXES OF CHROMIUM AND FLUORINATED CARBOXYLIC ACIDS [75} Inventors: Robert E. Dear, Mount Kisco, N.Y.;

Jai Prakash Tandon, Cranston, RI.

[731 Assignee: Ciba-Geigy Corporation, Ardsley,

22 Filed: Feb. 22, 1972 211 App]. No.: 228,395

[52] US. Cl 106/2; 106/13; 260/4385 C [51] Int. C1. C09K 3/18 [58] Field of Search 106/13, 2; 260/4385 C,

[56] References Cited UNITED STATES PATENTS 3,287,141 11/1966 Bartz 106/13 FOREIGN PATENTS OR APPLICATIONS 970.494 9/1964 United Kingdom 260/4385 C Primary Examiner-Lorenzo B. Hayes Attorney, Agent, or Firm.10seph G. Kolodny; Edward McC. Roberts; Prabodh 1. Almaula 5 Claims, No Drawings COMPOSITIONS CONTAINING WERNER COMPLEXES OF CHROMIUM AND FLUORINATED CARBOXYLIC ACIDS strate materials. Particularly desirable surface for treat-- merit are paper and leather.

More specifically the present disclosure concerns a composition containing separate Werner complexes formed from chromium and fluorinated carboxylic acids.

The use of specific fluorinated carboxylic acids to form a Werner complex with trivalent chromium is known in the prior art. Illustrativel y Reid, US. Pat, No. 2,662,835 and LaFleur US. Pat. No. 2,904,571 both disclose the initial utilization of a. fluorinated acid of the formula C F COOl-l in formation of a chromium complex.

In the present composition which is suitable for imparting oil and water repellency, two separate fluori' nated carboxylic acid types are used as source materials. An advantage of the present invention is that physical separation of the acid mixture need not take place prior to formation of the Werner complex.

The present invention employsthe Werner complex formed from trivalent chromium and a fluorinated carboxylic acid of the formula R,COOl-l as disclosed in US. Pat. Nos. 2,662,835 and 2,904,571. As employed herein, R, is a perfluoroalkyl group either straight or branched containing 3 to 18 carbon atoms. For maximum efficiency a straight chain R, group is preferable. Most desirably this fluorinated constituent will contain from 6 to 12 carbon atoms.

Also' in the composition of this disclosure an additional chromium complex is employed utilizing a starting acid of the formula type R,CH COOH, with R as defined; namely, a straight or branched chain containing 3 to 18 carbon atoms in the fluorinated group.

In comparison of chromium complexes prepared from acids of the type RyCOOH as opposed to the acid type R,CH COOH, the complex from R COOH- chromium is clearly superior at equivalent fluorine contents in providing oil and soil repellency. Thus this Werner complex is clearly more efficient in providing the desired degree of oil or water repellency.

However, it has been unexpectedly discovered that a mixture of chromium complexes from these two separate acids, namely, R,COOH and R,CH COOH gives results which are essentially similar as a more preferred chromium complex formedfrom RjCOOH. This comparison holds true on the basis of equal fluorine contents on the substrate.

As previously mentioned a mixture of acids of the type R,COOH and R,CH COOH can be utilized in conjunction with one anotherin forming a mixture of Werner complexes. in such a case these acids can be prepared in the presence of one another and no physical separation procedures need take place prior to preparation of the desired complexes.

The chromium complexes using a starting fluorinated carboxylic acid of the type RyCOOH are well known in the art such as evidenced by Reid, US. Pat. No. 2,662,835. r

The second starting acid of the type RjCH COOH is known in the prior art and a suitable method of preparation is disclosed in J. Org. Chem. 23, 1166 (1958).

2 The starting fluorinated acids may be formed from byproducts which arise from esterification of R,CH CH I with an acid in the presence of a base". Separation of the ester will leave an olefinbyproduct of the formula R CH=CH which is formed by dehydrohalo genation of the starting iodide. Also present with this olefin will be unseparated esters of the type R CH CH OCOR and starting material R,CH CH I. Oxidation of these byproducts with -the unseparated ester by well knowntechniques such as use of potassium dichromate (e.g., US. Pat. No. 3,525,758) or potassium permanganate will give R,COOH from the olefin as well as R,CH COOH from the unseparated ester and R,CH CH l starting material.

The preparation of the Werner complexes from trivalent chromium and the disclosed combination of fluorinated carboxylic acids involves known techniques such as disclosed in Reid US. Pat. No. 2,662,835. The preparation of a Werner complex involving the use of a fluorinated carboxylic acid and chromium is well documented in the prior art and similar methods may be utilized. Illustratively, chromyl. chloride may be reduced with an alcohol followed by reaction of the chromic compound with the fluorinated carboxylic acid.

A second method of preparation involves a hydrolysis of chromium chloride hexahydride with a basic hydroxide such as sodium hydroxide followed by a ,reaction of the chromium salt with the fluorinated carboxylic acid. This general method of preparation is described in US. Pat. No. 3,351,663. Other less desirable methods are described in US. Pat. No. 2,909,545.

The present composition containing a mixture of Werner complexes to provide oil and water repellency to a substrate-will be formed from acids of the types RfCOOH and R,CH COOH. The proportions of R,COOl-l to R;CH COOH to form the Werner complex may vary over wide ranges such as from 10 to 99 parts by weight of RJCOOH to to 1 part by.weight RJCHZCOOH. More desirably the RflOOl-l-chromium .complex will be present in a major proportion in comthough generally the ratio will be between 2:1 and 12:1

chromium to acid (mole ratio). Ata ratioof less than 2:1, precipitation occurs if the concentrated complex solution is diluted. At high chromium contents, the complexes will perform effectively but high loadings are required to obtain comparable results. A most pre ferred ratio of chromium to acid is between 2:1 and 4:1.

The type of substrate material to which the complexes are applied is not critical, although paper and leather are preferred substrates. Coatings may be.:applied to various surfaces such as textiles, leather, paper, wood, masonry, metal, plastics, glass, painted surfaces. and the like. These coatings may be readily applied by various coating techniques such as dipping, spraying,

brushing, padding, roller coating and the, like.

For the purposes of evaluation of the disclosed compositions, repellency ratings for both oil and water were examples involved, the repellency ratings were determined as follows:

3 For oil resistance (Kit Test) TAPPI Routine Control Test, RC No. 338 was employed. Briefly this test utilizes 12 solutions of various proportions of castor oil, toluene and heptane. The solutions are numbered from 1 to 12 in descending order as the amount of castor oil is decreased. A Kit value represents the highest number solution to stay on the paper surface for seconds in the form of a dropwithoutsurface penetration. A high number denotes superior oil resistance. 1

Water repellency is determined by TAPPI (Technical Association of the Pulp and Paper Industry) No.44]- OS-69 issued Dec. 1, 1969, and is known as the Cobb Size Test. Briefly this test is on the basis of water absorbed based on an area of one hundred square centimeters of the paper substrate. Low numerical values denote superior repellency.

The following examples describe the various innovative aspects of the present invention.

EXAMPLE 1 Z-Perfluoroalkyl ethyl iodide (800 g; 1.43 moles) (R, equals C 1? 27.1 percent, C F 59.4 percent and C F 12.2 percent), cadmium oxide (184 g; 1.43 mole) and acetic acid (2700 ml) were added to a stain-- less steel autoclave of 1 gallon capacity and heated with stirring to 180 for 19 hrs. The reactor was cooled and the crude product washed with water. The organic layer was separated, dissolved in chloroform and EXAMPLE 2 Potassium permanganate (112.5 g), tertiary-butanol (100 g) and water (70 g) were stirred and a distilled mixture comprising 2-perfluoroalkyl ethylene and perfluoroalkyl ethyl acetate was added at a rate sufficient to maintain thetemperature below 70. Stirring continued at a temperature of 70C for minutes. The mixture was'heated slowly to reflux temperature and was held at this temperature for 3 hrs. with continuous stirring. At the end of this time, denatured ethanol (5 g, 0.1 mole) was added at a rate sufficient to maintain constant reflux. The mixture was then diluted with water 250 g at 60C), filtered and the filter residue was washedwith water 125 g at 60C). The filter resi- 4 percent, C E =,1. 5percent, RflH CoOl-lz C F =0.1 percent, C F =7.1 percent, Ci E 49 percent).

EXAMPLES A 250 ml creased flask, with three necks, was fitted with a mechanical stirrer, condenser with dryin'g tube, addition funnel, nitrogen inlet and a thermometer extending below the liquid surface. The composition in Example 2 (25.4 g; 0.05 mole) dissolvedin 75 ml dry isopropanol (dried over molecular sieves) and added re the flask. Chrornyl chloride;(-25.0 g; 0.161 mole)'was dissolved-in carbon tetrachloride (70 ml) and placed in theaddition funnel (this solution must be mixed thoroughly, otherwise the Co c1 will tend to forth a lower layer) "andthen added slowly, with stirring. The rate of addition was adjusted so that the exothermic reaction maintained the temperature between 40C and 60C. Then the system, was; refluxed and stirred for one hour. After cooling, any solid'impurities were removed by filtration and the carbon tetrachloride wastaken ofi'on the rotary evaporaton-The solu I tion was adjusted to 30 percent solids with i'sopropanol and 1 ml water was added as a stabilizer.

,. Q I, This procedure involves a 3:1 ratio of chromium compoundto acid. I w H I EXAMPLES 4 to s A 250 ml three-necked creased flask is fitted with a mechanical stirrer, a condenser and a dropping funnel. Chromium chloride hexahydrate (CrCl 61-1 0) (34 g; 0.128 mole) is dissolved in ml. isopropanol in the flask and a solution of sodium hydroxide (5.2 g', 0.130

mole) is prepared'in 30 g methanol. With rapid stirring, the alcoholic base is added to the isopropanol solution of CrCl 6H O. A precipitate of sodium chloride forms and the reaction'is completed by heating to reflux temperature for 1 hr The slurry is cooled and a mixture of fluoro acid (0.04moles in 10 ml i sopropanol) is added" slowly, with stirring, at ambient temperatures. This acid mixture comprises R COOH: containing C F 5.9 percent, C F 42.2 percent, C 1 21.6 p ercent;' and 3 percent, C F CH 6.1 percent C QF CHQ 5.3 percent. The solu tion is refluxed briefly, then cooled and filtered. At this stage, the methanol may, if it is so desired, be removed by distillation. The 3 .1 complex is'then adjusted to 30 I R CH COOH containing C F CH 11.1

percent solids 'with isopropanol. In'similar fashion using the acid composition previously described, complexes were obtained at chr omium to acid ratios of 2:1,451, 5:1 and 61:1 respectively.

EX. Acid Ratio c ncoou 5 29.7g. 0.05 mole 266g, 0.10 mole 4.2g, 0.l05 mole H 2:1 6 14.82g, 0.025 mole 266g, 0.10 mole 4.2g, 0.105 mole 4:1 7 23.7g, 0.04 mole 53.2 ,0.20me1e s.0 ,0.20mele' 5:1 8 19.8g, 0.033 mole 53.2g, 0.20 mole 's.0 ,0.20 mole 6;]

due was discarded while the filtrate and water wash were combined and acidifi'ed'with 37 ercent h drop y EXAMPLE 9 chloric acid (80 g, 0.80 mole) After standing for 1 hr., the lower fluorocarbon phase was separated and washed with 50 g of water. The crude fluorocarbon acid phase 'was stripped under reduced pressure at C and 25 mm Hg to remove tertiary-butanol and water to give perfluoroalkanoic acids (57 g, RICOOHZ C F =2.3 percent, C F =4L6 percent, C F =31.7

The procedure of Example followed except that the acid type R,COOH was employed where" R C F 23.6 percent, C F 52.1 percent and C F 19.4percent by weight. R,C1-I COOH was present as an impurity but was present at less than 1% by weight. 22.8 grams (0.05 mole) of RJCOOH was used .while 6 25.0 g (0.161 mole) of chromyl chloride was employed TABLE 2 to give a ratio of Cr to R,COOH of 3: 1.

Cobb Size Test (water resistance) (g. water absorbed/100 cm EXAMPLE 10 %F owp* To prepare a R CH COOH type acid, a mixed alco- Test Material 0J2 016 020 hol, R CH Cl-l Ol-l (50 g) (R,=20.7 percent C F 44.6 3 l C C I f I 1' 0m X 0 percent C F and 28.9 percent C F was added grad- RICOOH/REHZCOOH mixture Q40 025 0.24 024 ually to potassium permanganate (100 g; 6 mole) ter- 3:1 Cr Complex of R,c001-1 tiary butyl alcohol (100 g) and water (75 ml) at a rate 3:1 Cr Complex of such that the temperature of the reactor dld not exceed RCHZCOOHM 0, 4 0,51 0,52 0, 0 70. The mixture was slowly warmed to reflux tempera- 311 Cf Complex ture and held there for 3 hrs. Stirring was maintained 1212518 throughout. The mixture then was cooled, diluted with Untreated Paper absorbs Q7 s "2 1 water and filtered. The filter residue was washed thor- I 5 zz fig g grz oughly with water and discarded. The filtrate and wash- 'mixture f Ex. 9

ings were combined and acidified with concentrated M hydrochloric acid, at which time a lower fluorocarbon layer separated. This was separated, washed with water TABLE 3 and the t-butyl alcohol was removed by distillation, giv- Effect of Chromium to Acid Ratio Variations in ing a mixture of 1,l-dihydroperfluoroalkanoic acids, R OOH /R H COOHU C l C K T l R,CH COOH, 30 g) ,=2s.9 percent c 5 44.0 perp 2 533533;) omparame est cent C,;F and 26.6 percent C F Chromium: Acid F owp* l 1 Ratio 0.08 0.12 0.16 0.20

2-1 7 10 12 12 In similar fashion as Example 4, a 3:1 chromium 7 10 H 12 complex of Y R CH COOH was obtained using 4:1 6 8 10 12 CrCl 6H O 34.0 g; 0.128 mole); NaOH 5.2 g; 0.130 if} g g g mole) and R,CH COOH (16.5 g; 0.04 mole).

*on weight of paper mixture of Ex. 4

The chromium complexes of Example 4, Example 9 and Example 1 1 at ratios of 3:1 chromium to acid were TA LE 4 evaluated at varying fluorine contents on paper made Effect of Chromium to Add Ratio Variations in from 50 percen b h Sulfite p p and 50 percent R/COOH/REHZCOOH" Mixtures; Cobb Size Test (water resistance) rag. Also to serve as a comparison basis, a commer- Water absorbed/ 100 cially obtainable fluorinated carboxylic acid chromium Chromium; Acid %F s complex was used which is described in No. 121.2518 Ratio 0.08 0.12 0.16 0.20

of the Food Additive Regulations of the FDA. The 039 O23 O25 Q24 chromium to acid content is essentlally at a mole ratio 3=1 0.40 0.25 0.24 0.24

The complexes were applied to a paper surface by 053 ,49 04 padding at fluorine weight levels at 0.08, 0.12, 0.16 and on weight of paper 0.20 percent. The resistance to oil was determined in mixture f 4 accordance with TAPPI Routine Control Test RC No. 338 and the resistance of the paper to water was determined in accordance with TAPPI, Official Bulletin, No. T 44l-OS-69.

The following tables summarize the results obtained:

While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not to be limited thereto but is to be con- 50 strued broadly within the scope and extent of the appended claims.

TABLE 1 What is claimed is: Comparadvc Kit Test (on resistance) 1. A water and oil-repellent composition containing a "/(F owp* solvent and Werner type complexes prepared by react ing trivalent chromium with a mixture of Test materlal 0.04 0.08 0.12 0.16 0.20

a. a fluorinated acid of the type R,COOH, and 3:1 Cr Complex of RCOOHIRICHZCOOH 4 7 l0 1 l 12 b. a fluorinated acid of the type R,CH COOH. mixture wherein R, is a perfluoroalkyl group of 3 to 18 car 3:1 Cr CQmPleX of l7 l2 bon atoms and the mole ratio of chromium to acid gf g g i 6 9 l2 types a and b is between 2:1 and 4:1, said composi- R1CH,COOH 5 7 8 9 10 tion containing from 10 to 99 parts by weight of z 4 6 6 6 6 RJCOOH and correspondingly from 90 to 1 part by weight of apu coou. Untreated paper ives 4 Kit Number r 2. The composition of claim 1 wherein R f is a perfluonlz tf g g f f roalky] group of 6 to 12 carbon atoms. 'mixture of Ex. 9 3. The composition of claim 1 wherein the fluorinated constituent of acid types a and b are of different chain lengths.

i $907,576: i i I by: 8 a 4. The-(go osition; wherein the ratio be- 5. The composition of claim 4 wherein said ratio is andRyCI-lCOOl-l is not more than 9:1 not more than 4:1. ffi i h 

1. A WATER AND OIL-REPELLENT COMPOSITION CONTAINING A SOLVENT AND WENER TYPE COMPLEXES PREPARED BY REACTING TRIVALENT CHROMIUM WITH A MIXTURE OF A. A FLUORINATED ACID OF THE TYPE RFCOOH, AND B. A FLUORINATED ACID OF THE TYPE RFCH2 COOH, WHEREIN RF IS A PERFLUOROALKYL GROUP OF 3 TO 18 CARBON ATOMS AND THE MOLE RATIO OF CHROMIUM TO ACID TYPES A AND B IS BETWEEN 2:1 AND 4:1, SAID COMPOSITION CONTAINING FROM 10 TO 99 PARTS BY WEIGT OF RFCOOH AND CORRESPONDINGLY FROM 90 TO 1 PART BY WEIGHT OF RFCH2COOH.
 2. The composition of claim 1 wherein Rf is a perfluoroalkyl group of 6 to 12 carbon atoms.
 3. The composition of claim 1 wherein the fluorinated constituent of acid types a and b are of different chain lengths.
 4. The composition of claim 1 wherein the ratio between RfCOOH and RfCH2COOH is not more than 9:1 by weight.
 5. The composition of claim 4 wherein said ratio is not more than 4:1. 